US20050019658A1 - Alkali cell - Google Patents

Alkali cell Download PDF

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Publication number
US20050019658A1
US20050019658A1 US10/500,899 US50089904A US2005019658A1 US 20050019658 A1 US20050019658 A1 US 20050019658A1 US 50089904 A US50089904 A US 50089904A US 2005019658 A1 US2005019658 A1 US 2005019658A1
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United States
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manganese dioxide
potential
battery
nickel oxyhydroxide
positive electrode
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Abandoned
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US10/500,899
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English (en)
Inventor
Shigeto Noya
Yasuo Mukai
Michiko Fujiwara
Yuji Mototani
Hidekatsu Izumi
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Panasonic Corp
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Individual
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Assigned to MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD. reassignment MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MOTOTANI, YUJI, MUKAI, YASUO, FUJIWARA, MICHIKO, IZUMI, HIDEKATSU, NOYA, SHIGETO
Publication of US20050019658A1 publication Critical patent/US20050019658A1/en
Assigned to PANASONIC CORPORATION reassignment PANASONIC CORPORATION CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/24—Electrodes for alkaline accumulators
    • H01M4/32—Nickel oxide or hydroxide electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/24—Alkaline accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/06—Electrodes for primary cells
    • H01M4/08—Processes of manufacture
    • H01M4/12—Processes of manufacture of consumable metal or alloy electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M6/00—Primary cells; Manufacture thereof
    • H01M6/04—Cells with aqueous electrolyte
    • H01M6/06—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid
    • H01M6/08—Dry cells, i.e. cells wherein the electrolyte is rendered non-fluid with cup-shaped electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to an improvement of an alkaline battery that utilizes manganese dioxide and nickel oxyhydroxide as positive electrode active materials.
  • Alkaline batteries such as alkaline dry batteries comprise, for example, a positive electrode case which also serves as a positive electrode terminal, a cylindrical positive electrode mixture which is closely fitted to the inner face of the case, and a gelled negative electrode which is disposed in a hollow space of the positive electrode mixture with a separator interposed therebetween.
  • alkaline batteries including manganese dioxide and nickel oxyhydroxide as positive electrode active materials have inferior storage performance to alkaline batteries including no nickel oxyhydroxide, and have large self-discharge especially when stored at high temperatures.
  • the alkaline batteries including nickel oxyhydroxide have such a problem that the heavy load discharge performance thereof is inferior to that of the alkaline batteries including no nickel oxyhydroxide.
  • the normal electrode potential of nickel oxyhydroxide is 0.49 V relative to a normal hydrogen electrode (NHE (25° C.)), and the normal electrode potential of manganese dioxide is 0.15 V relative to an NHE (25° C.).
  • the potential of nickel oxyhydroxide in a KOH aqueous solution (KOH concentration 40 wt %) is 370 to 410 mV relative to an Hg/HgO electrode
  • the potential of electrolytic manganese dioxide in a KOH aqueous solution (KOH concentration 40 wt %) is, for example, 240 to 270 mV relative to an Hg/HgO electrode.
  • Electrolytic manganese dioxide having such a potential is generally used in conventional alkaline batteries including no nickel oxyhydroxide (Japanese Laid-Open Patent Publication No. Hei 7-183032).
  • the potential of manganese dioxide is designed in consideration of storage characteristics of batteries.
  • the potential of manganese dioxide is high, the potential difference between a positive electrode and a negative electrode including zinc as an active material becomes large. This allows the oxidation reaction of manganese dioxide to proceed readily even while the battery is not used, thereby inviting deterioration in storage characteristics.
  • the potential difference between the negative electrode and the positive electrode becomes large, the open circuit voltage of the battery becomes high.
  • a major improvement in voltage maintaining characteristics and high rate discharge characteristics is not observed. Therefore, manganese dioxide having a potential of approximately 250 mV which is not too high and not too low has become predominant.
  • An object of the present invention is to provide an alkaline battery capable of retaining heavy load discharge performance even after a long-term storage at high temperatures.
  • An alkaline battery in accordance with the present invention comprises: a positive electrode mixture comprising manganese dioxide and nickel oxyhydroxide as active materials; a negative electrode comprising zinc as an active material; and an alkaline electrolyte, and is characterized in that the potential of the manganese dioxide relative to a mercury/mercury oxide electrode (Hg/HgO electrode) in a potassium hydroxide aqueous solution having a KOH concentration of 40 wt % is 270 mV or higher.
  • Hg/HgO electrode mercury/mercury oxide electrode
  • the content of the manganese dioxide be from 20 to 90 wt % and that the content of the nickel oxyhydroxide be from 10 to 80 wt %.
  • manganese dioxide it is possible to use electrolytic manganese dioxide of which potential is heightened by cleaning with an aqueous solution of sulfuric acid.
  • the concentration of sulfuric acid in the aqueous solution of sulfuric acid is preferably 10 wt % or higher.
  • FIG. 1 is a partially sectional front view of an example of an alkaline battery in accordance with the present invention.
  • the potential difference between manganese dioxide and nickel oxyhydroxide needs to be reduced to avoid deterioration of nickel oxyhydroxide caused by the formation of the local battery.
  • it is effective to heighten the potential of manganese dioxide and bring it close to the potential of nickel oxyhydroxide.
  • manganese dioxide having a relatively low potential of approximately 250 mV relative to an Hg/HgO electrode in a KOH aqueous solution has conventionally been used also in alkaline batteries to which nickel oxyhydroxide is added to improve heavy load discharge performance. This is presumably because the potential of manganese dioxide has been selected based on the above-described technically common knowledge about conventional alkaline batteries including no nickel oxyhydroxide without sufficient awareness that the formation of the local battery causes deterioration of nickel oxyhydroxide.
  • manganese dioxide having a potential of 270 mV or higher relative to an Hg/HgO electrode in a KOH aqueous solution (KOH concentration 40 wt %). This is because the use of such manganese dioxide makes it possible to reduce the potential difference between the nickel oxyhydroxide generally used in alkaline batteries and the manganese dioxide down to a level at which the above-described oxidation reduction reaction is suppressed.
  • the manganese dioxide having a potential of 270 mV or higher relative to an Hg/HgO electrode in a KOH aqueous solution may be prepared, for example, by electrolyzing a solution containing divalent manganese ions.
  • the potential of manganese dioxide is varied by controlling electrolytic potential, manganese ion concentration, sulfuric acid concentration, current density, solution temperature, etc (Japanese Laid-Open Patent Publication No. 2002-348693).
  • electrolytic manganese dioxide having a desired potential by properly selecting electrolytic conditions.
  • manganese dioxide having low potential is cleaned with sulfuric acid, lower level manganese oxides on the surfaces of manganese dioxide particles are dissolved and removed, so that manganese dioxide having higher potential can be obtained.
  • electrolytic manganese dioxide is mixed with an aqueous solution of sulfuric acid to produce slurry.
  • concentration of manganese dioxide in the produced slurry is preferably from 100 to 300 g/L.
  • the sulfuric acid concentration of the aqueous solution of sulfuric acid used therein is preferably 5 wt % or higher and more preferably 10 wt % or higher.
  • the electrolytic manganese dioxide used therein normally has a purity of 91 to 92% with inclusion of impurities such as lower level manganese oxides, water and sulfate.
  • the slurry is stirred for 5 to 10 hours while the temperature thereof is maintained at 45° C. to 60° C. Thereafter, manganese dioxide is filtered out, washed with water, and neutralized with alkali if necessary and washed again. By these steps, the potential of manganese dioxide is heightened.
  • the positive electrode mixture is prepared by mixing manganese dioxide with heightened potential and nickel oxyhydroxide together with a conductive material such as graphite and an alkaline aqueous solution.
  • the average particle size of manganese dioxide is preferably from 30 to 50 ⁇ m, and the average particle size of nickel oxyhydroxide is preferably from 5 to 30 ⁇ m.
  • the content of manganese dioxide be from 20 to 90 wt % and that the content of nickel oxyhydroxide be from 10 to 80 wt %.
  • the discharge performance of the alkaline battery at initial stage is further improved.
  • FIG. 1 merely illustrates an example of the alkaline battery of the present invention and is not to be construed as limiting the present invention.
  • a positive electrode case 1 is made of steel plated with nickel.
  • a graphite coating film 2 is formed on the inner face of the positive electrode case 1 .
  • a plurality of positive electrode mixture pellets 3 in a short cylindrical shape are inserted into the positive electrode case 1 so as to intimately contact the inner face of the case 1 .
  • a separator 4 is provided in the hollow space of the positive electrode mixture pellets 3 , and an insulating cap 5 is provided in the central part of the bottom of the case 1 .
  • the separator 4 and the positive electrode mixture pellets 3 are impregnated with an alkaline electrolyte.
  • a negative electrode current collector 10 is inserted into the central part of the gelled negative electrode 6 .
  • the negative electrode current collector 10 is pressed into a central hole of a resin sealing plate 7 , and is integrally welded, at the head thereof, to a bottom plate 8 .
  • the bottom plate 8 also functions as a negative electrode terminal.
  • An insulating washer 9 is caught by the sealing plate 7 .
  • the opening end of the positive electrode case 1 is crimped onto the outer edge of the bottom plate 8 with the outer edge of the resin sealing plate 7 interposed therebetween. Thus, the opening of the positive electrode case 1 is sealed.
  • the outer surface of the positive electrode case 1 is covered with a jacket label 11 .
  • HH-PF electrolytic manganese dioxide for alkaline batteries manufactured by Tosoh Corporation.
  • the physical properties of HH-PF are shown below.
  • This electrolytic manganese dioxide was mixed with an aqueous solution of sulfuric acid having a sulfuric acid concentration of 5 wt % to produce slurry of 60° C.
  • the concentration of manganese dioxide in the slurry was 100 g/L.
  • the slurry was stirred for one hour while it was maintained at 60° C., and thereafter, manganese dioxide was filtered out and washed with water. Then, the washed manganese dioxide was washed with an aqueous solution of sodium hydroxide to neutralize the remaining sulfuric acid and washed again with water.
  • the Manganese dioxide with heightened potential, nickel oxyhydroxide (average particle size 10 ⁇ m), and graphite (average particle size 20 ⁇ m) were mixed in a weight ratio of 50:50:5. Further, 1 part by weight of an alkaline electrolyte per 100 parts by weight of the total of manganese dioxide and nickel oxyhydroxide was added to the above-described mixture, and the resultant mixture was stirred with a mixer and granulated to have a certain particle size.
  • the alkaline electrolyte used was an aqueous solution of potassium hydroxide having a KOH concentration of 40 wt %. The particles thus obtained were pressurized into a hollow cylindrical shape to mold positive electrode mixture pellets A.
  • a plurality of positive electrode mixture pellets A thus obtained were charged into a positive electrode case, and the pellets A were pressed again inside the case so as to intimately contact the inner face of the case. Subsequently, a separator was fitted to the inner face of the hollow space of the positive electrode mixture pellets A, and an insulating cap was provided in the central part of the bottom of the case. Then, an alkaline electrolyte (an aqueous solution of potassium hydroxide having a KOH concentration of 40 wt %) was injected into the case to impregnate the separator and the positive electrode mixture pellets A.
  • an alkaline electrolyte an aqueous solution of potassium hydroxide having a KOH concentration of 40 wt % was injected into the case to impregnate the separator and the positive electrode mixture pellets A.
  • Batteries at the initial stage and after a 7-day storage at 60° C. were continuously discharged at a constant electric power of 1000 mW at 20° C., and discharge duration was measured until the battery voltage reached to a cut-off voltage of 0.9 V. Also, the ratio (%) of the discharge duration of the battery after the storage to the discharge duration of the battery at the initial stage was obtained.
  • the potential of manganese dioxide was heightened in the same manner as in Example 1 except that the concentration of sulfuric acid in the aqueous solution of sulfuric acid was changed from 5 wt % to 10 wt %, 15 wt %, 20 wt % and 30 wt %.
  • positive electrode mixture pellets B, C, D and E were produced in the same manner as in Example 1 except for the use of the electrolytic manganese dioxide “b”, “c”, “d” and “e”.
  • batteries B, C, D and E were produced in the same manner as in Example 1 except for the use of the positive electrode mixture pellets B, C, D and E, and were evaluated in the same manner as the battery A.
  • Positive electrode mixture pellets F were produced in the same manner as in Example 1 except that HH-PF, electrolytic manganese dioxide for alkaline batteries manufactured by Tosoh Corporation, was used without any treatment. Then, a battery F was produced in the same manner as in Example 1 except for the use of the positive electrode mixture pellets F and was evaluated in the same manner as the battery A.
  • HH-TF electrolytic manganese dioxide for alkaline batteries manufactured by Tosoh Corporation.
  • the physical properties of HH-TF are shown below.
  • positive electrode mixture pellets G were produced in the same manner as in Example 1 except for the use of the electrolytic manganese dioxide “g”.
  • a battery G was produced in the same manner as in Example 1 except for the use of the positive electrode mixture pellets G and was evaluated in the same manner as the battery A.
  • Table 1 shows potentials of the manganese dioxide “a” to “g” and discharge durations of the batteries A to G. It is noted that each discharge duration is an average value of ten batteries which is expressed as a relative value obtained by defining the discharge duration at the initial stage of the battery F in Comparative Example 1 as 100. TABLE 1 Electrode potential Sulfuric acid of Discharge duration Battery concentration manganese Initial After (B/A) ⁇ 100 No.
  • the batteries A to E which used manganese dioxide having a potential of 270 mV or higher, had an improved discharge performance after high temperature storage in comparison with the battery F, which used manganese dioxide having a potential lower than 270 mV.
  • the higher the sulfuric acid concentration of the aqueous solution of sulfuric acid the higher the potential of the resultant manganese dioxide.
  • the higher the sulfuric acid concentration of the aqueous solution of sulfuric acid the higher the ratio of the discharge duration of the battery after storage to the discharge duration of the battery at the initial stage.
  • Positive electrode mixture pellets were produced in the same manner as in Example 1 except that HH-PF, electrolytic manganese dioxide for alkaline batteries manufactured by Tosoh Corporation, was used without any treatment and that the contents of manganese dioxide and nickel oxyhydroxide in the positive electrode mixture were varied as shown in Table 2, and batteries 1 to 8 were assembled. Then, the batteries 1 to 8 were evaluated in the same manner as the battery A of Example 1.
  • Table 2 shows discharge durations of the batteries 1 to 8 . It is noted that each discharge duration is an average value of ten batteries which is expressed as a relative value obtained by defining the discharge duration at the initial stage of the battery 1 as 100. TABLE 2 Content in positive electrode (part by weight) Discharge duration Battery Manganese Nickel Initial After (B/A) ⁇ 100 No.
  • HH-PF electrolytic manganese dioxide for alkaline batteries manufactured by Tosoh Corporation
  • the potential of this electrolytic manganese dioxide was heightened in the same manner as in Example 1 except for the use of an aqueous solution of sulfuric acid having a sulfuric acid concentration of 15 wt %, thereby producing manganese dioxide whose potential relative to an Hg/HgO electrode in a KOH aqueous solution (KOH concentration 40 wt %) was 288 mV.
  • Positive electrode mixture pellets were produced in the same manner as in Example 1 except that the manganese dioxide thus obtained was used and that the contents of manganese dioxide and nickel oxyhydroxide in the positive electrode mixture were varied as shown in Table 3, and batteries 9 to 14 were assembled. Then, the batteries 9 to 14 were evaluated in the same manner as the battery A of Example 1.
  • Table 3 shows discharge durations of the batteries 9 to 14 . It is noted that each discharge duration is an average value of ten batteries which is expressed as a relative value obtained by defining the discharge duration at the initial stage of the battery 1 in Comparative Example 2 as 100.
  • HH-TF electrolytic manganese dioxide for alkaline batteries manufactured by Tosoh Corporation.
  • the potential of this electrolytic manganese dioxide was heightened in the same manner as in Example 1, thereby producing manganese dioxide whose potential relative to an Hg/HgO electrode in a KOH aqueous solution (KOH concentration 40 wt %) was 283 mV.
  • Positive electrode mixture pellets were produced in the same manner as in Example 1 except that the manganese dioxide thus obtained was used and that the contents of manganese dioxide and nickel oxyhydroxide in the positive electrode mixture were varied as shown in Table 4, and batteries 15 to 20 were assembled. Then, the batteries 15 to 20 were evaluated in the same manner as the battery A of Example 1.
  • Table 4 shows discharge durations of the batteries 15 to 20 . It is noted that each discharge duration is an average value of ten batteries which is expressed as a relative value obtained by defining the discharge duration at the initial stage of the battery 1 in Comparative Example 2 as 100. TABLE 4 Content in positive electrode (part by weight) Discharge duration Battery Manganese Nickel Initial After (B/A) ⁇ 100 No. dioxide oxyhydroxide Graphite stage(A) storage(B) (%) 15 95 5 5 105 93 89 16 90 10 5 113 104 92 17 80 20 5 124 109 88 18 50 50 5 144 114 79 19 20 80 5 150 105 70 20 10 90 5 157 86 55 (Cut-off voltage 0.9 V)
  • the improvements in storage characteristics were particularly remarkable when the content of manganese dioxide with respect to the total amount of manganese dioxide and nickel oxyhydroxide was from 20 to 90 wt % and the content of nickel oxyhydroxide was from 10 to 80 wt %.
  • an alkaline battery comprising manganese dioxide and nickel oxyhydroxide as active materials and retain heavy load discharge performance of the alkaline battery even after storage.

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  • Chemical Kinetics & Catalysis (AREA)
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US10/500,899 2002-02-07 2003-01-29 Alkali cell Abandoned US20050019658A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2002-30515 2002-02-07
JP2002030515A JP3873760B2 (ja) 2002-02-07 2002-02-07 アルカリ電池
PCT/JP2003/000860 WO2003067689A1 (fr) 2002-02-07 2003-01-29 Pile alcaline

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US20050019658A1 true US20050019658A1 (en) 2005-01-27

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US (1) US20050019658A1 (de)
EP (1) EP1473788B1 (de)
JP (1) JP3873760B2 (de)
KR (1) KR20040079984A (de)
CN (1) CN100391036C (de)
AT (1) ATE411623T1 (de)
AU (1) AU2003244343B2 (de)
BR (1) BR0306703A (de)
CA (1) CA2474164A1 (de)
DE (1) DE60324098D1 (de)
HK (1) HK1068029A1 (de)
WO (1) WO2003067689A1 (de)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040248007A1 (en) * 2003-06-09 2004-12-09 Hiromi Tamakoshi Positive electrode for alkaline battery and alkaline battery using the same
US20070166614A1 (en) * 2004-06-24 2007-07-19 Fumio Kato Alkaline battery
US20070287066A1 (en) * 2006-06-07 2007-12-13 Tadaya Okada Alkaline primary battery
US20080026285A1 (en) * 2004-06-23 2008-01-31 Katsuya Sawada Alkaline Battery
US20080193847A1 (en) * 2007-02-14 2008-08-14 Tosoh Corporation Electrolytic manganese dioxide, and method for its production and its application
US20090023077A1 (en) * 2006-08-10 2009-01-22 Fumio Kato Alkaline battery
US20090047578A1 (en) * 2007-08-10 2009-02-19 Hitachi Maxell, Ltd. Positive electrode for alkaline battery and alkaline battery using the same
US20090263710A1 (en) * 2008-04-18 2009-10-22 Fumio Kato Aa alkaline battery
US20100068620A1 (en) * 2006-11-22 2010-03-18 Jun Nunome Alkaline battery
US20100099028A1 (en) * 2008-10-17 2010-04-22 Shinichi Sumiyama Alkaline battery
US20100297493A1 (en) * 2008-10-01 2010-11-25 Michiko Fujiwara Alkaline battery
US20120141361A1 (en) * 2009-08-24 2012-06-07 Tosoh Corporation Electrolytic manganese dioxide, and method for its production and its application
EP2545606B1 (de) * 2010-03-12 2019-05-22 Duracell U.S. Operations, Inc. Verfahren zur herstellung von säurebehandeltem mangandioxid

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7273680B2 (en) * 2002-08-28 2007-09-25 The Gillette Company Alkaline battery including nickel oxyhydroxide cathode and zinc anode
US7435395B2 (en) 2003-01-03 2008-10-14 The Gillette Company Alkaline cell with flat housing and nickel oxyhydroxide cathode
WO2005015666A1 (ja) * 2003-08-06 2005-02-17 Matsushita Electric Industrial Co., Ltd. アルカリ電池
AU2005224903B2 (en) * 2004-03-24 2006-11-23 Matsushita Electric Industrial Co., Ltd. Alkaline battery
JP4993887B2 (ja) * 2004-09-09 2012-08-08 三井金属鉱業株式会社 正極活物質用マンガン酸化物粉体
JP2006156309A (ja) * 2004-12-01 2006-06-15 Fdk Energy Co Ltd 携帯電話機用乾電池式充電器
JPWO2007037181A1 (ja) 2005-09-27 2009-04-09 パナソニック株式会社 アルカリ乾電池
EP1777760A1 (de) * 2005-10-21 2007-04-25 Matsushita Electric Industrial Co., Ltd. Alkalibatterie
JP5081387B2 (ja) * 2006-01-12 2012-11-28 Ｆｄｋエナジー株式会社 正極合剤およびアルカリ電池
JP5428163B2 (ja) * 2007-02-14 2014-02-26 東ソー株式会社 アルカリマンガン乾電池用電解二酸化マンガン及びその製造方法並びにその用途
JP2008210719A (ja) 2007-02-27 2008-09-11 Seiko Instruments Inc 扁平形アルカリ一次電池
JP2008210720A (ja) 2007-02-27 2008-09-11 Seiko Instruments Inc 扁平形アルカリ一次電池
JP2010282744A (ja) * 2009-06-02 2010-12-16 Panasonic Corp アルカリ乾電池
JP5909845B2 (ja) * 2009-08-24 2016-04-27 東ソー株式会社 電解二酸化マンガン及びその製造方法並びにその用途
CN102544470A (zh) * 2012-03-12 2012-07-04 苏州大学 碱锰电池的正极材料、碱锰电池正极和碱锰电池

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6214198B1 (en) * 1998-12-21 2001-04-10 Kerr-Mcgee Chemical Llc Method of producing high discharge capacity electrolytic manganese dioxide
US6235428B1 (en) * 1997-01-30 2001-05-22 Sanyo Electric Co., Ltd. Enclosed alkali storage battery
US20010031239A1 (en) * 1998-12-21 2001-10-18 Andersen Terrell Neils High discharge capacity electrolytic manganese dioxide and methods of producing the same
US20020046955A1 (en) * 2000-09-01 2002-04-25 Tosoh Corporation Powder of electrolytic manganese dioxide and process for producing the same
US6566009B1 (en) * 1998-10-08 2003-05-20 Matsushita Electric Industrial Co., Ltd. Alkaline battery

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05151957A (ja) * 1991-11-29 1993-06-18 Toshiba Battery Co Ltd アルカリ電池
JP2806233B2 (ja) * 1993-11-10 1998-09-30 東ソー株式会社 電解二酸化マンガン及びその製造方法
JP4742468B2 (ja) * 2000-09-01 2011-08-10 東ソー株式会社 電解二酸化マンガン粉末及びその製造法
JP4882163B2 (ja) * 2001-05-15 2012-02-22 ソニー株式会社 アルカリ亜鉛電池用正極およびアルカリ亜鉛電池

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6235428B1 (en) * 1997-01-30 2001-05-22 Sanyo Electric Co., Ltd. Enclosed alkali storage battery
US6566009B1 (en) * 1998-10-08 2003-05-20 Matsushita Electric Industrial Co., Ltd. Alkaline battery
US6214198B1 (en) * 1998-12-21 2001-04-10 Kerr-Mcgee Chemical Llc Method of producing high discharge capacity electrolytic manganese dioxide
US20010031239A1 (en) * 1998-12-21 2001-10-18 Andersen Terrell Neils High discharge capacity electrolytic manganese dioxide and methods of producing the same
US6638401B1 (en) * 1998-12-21 2003-10-28 Kerr-Mcgee Chemical Llc High discharge capacity electrolytic manganese dioxide and methods of producing the same
US20020046955A1 (en) * 2000-09-01 2002-04-25 Tosoh Corporation Powder of electrolytic manganese dioxide and process for producing the same

Cited By (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040248007A1 (en) * 2003-06-09 2004-12-09 Hiromi Tamakoshi Positive electrode for alkaline battery and alkaline battery using the same
US20080026285A1 (en) * 2004-06-23 2008-01-31 Katsuya Sawada Alkaline Battery
US20070166614A1 (en) * 2004-06-24 2007-07-19 Fumio Kato Alkaline battery
US20070287066A1 (en) * 2006-06-07 2007-12-13 Tadaya Okada Alkaline primary battery
US20090023077A1 (en) * 2006-08-10 2009-01-22 Fumio Kato Alkaline battery
US20100068620A1 (en) * 2006-11-22 2010-03-18 Jun Nunome Alkaline battery
EP1964944A1 (de) * 2007-02-14 2008-09-03 Tosoh Corporation Elektrolytisches Mangan-Dioxid und Verfahren zu dessen Herstellung und Anwendung
US8734992B2 (en) 2007-02-14 2014-05-27 Tosoh Corporation Electrolytic manganese dioxide, and method for its production and its application
US8721865B2 (en) 2007-02-14 2014-05-13 Tosoh Corporation Electrolytic manganese dioxide, and method for its production and its application
US20080193847A1 (en) * 2007-02-14 2008-08-14 Tosoh Corporation Electrolytic manganese dioxide, and method for its production and its application
US8153298B2 (en) 2007-08-10 2012-04-10 Hitachi Maxell Energy, Ltd. Positive electrode for alkaline battery and alkaline battery using the same
US20090047578A1 (en) * 2007-08-10 2009-02-19 Hitachi Maxell, Ltd. Positive electrode for alkaline battery and alkaline battery using the same
US20090263710A1 (en) * 2008-04-18 2009-10-22 Fumio Kato Aa alkaline battery
US8241780B2 (en) * 2008-10-01 2012-08-14 Panasonic Corporation Alkaline battery
US20100297493A1 (en) * 2008-10-01 2010-11-25 Michiko Fujiwara Alkaline battery
US7820326B2 (en) 2008-10-17 2010-10-26 Panasonic Corporation Alkaline battery
US20100099028A1 (en) * 2008-10-17 2010-04-22 Shinichi Sumiyama Alkaline battery
US20120141361A1 (en) * 2009-08-24 2012-06-07 Tosoh Corporation Electrolytic manganese dioxide, and method for its production and its application
US9103044B2 (en) * 2009-08-24 2015-08-11 Tosoh Corporation Electrolytic manganese dioxide, and method for its production and its application
EP2545606B1 (de) * 2010-03-12 2019-05-22 Duracell U.S. Operations, Inc. Verfahren zur herstellung von säurebehandeltem mangandioxid

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CN1628393A (zh) 2005-06-15
JP2003234107A (ja) 2003-08-22
EP1473788B1 (de) 2008-10-15
CA2474164A1 (en) 2003-08-14
AU2003244343A1 (en) 2003-09-02
ATE411623T1 (de) 2008-10-15
EP1473788A1 (de) 2004-11-03
WO2003067689A1 (fr) 2003-08-14
KR20040079984A (ko) 2004-09-16
BR0306703A (pt) 2004-12-28
AU2003244343B2 (en) 2007-07-26
JP3873760B2 (ja) 2007-01-24
DE60324098D1 (de) 2008-11-27

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